Oxyalkylated phenol-aldehyde resin



' QAJLJPA W warm United States hatent 'iee;

No. 478,921. Divided and this application Oct. 16, 1956, Ser. No. 616,148

3 Claims. (Cl. 260-53) No Drawing. Original application Dec,- 30, 1954, Se

This invention relates to processes particularly adapted for breaking or resolving emulsions of the water-in-oil type. More particularly, this invention relates to processes of treating crude oil containing water, brine or sludge-like materials dispersed in a substantially permanent state throughout the oil, to break this state thereby permitting simple resolution and separation of the components of the material treated.

Emulsifying agents are broadly classified into two categories, those which stabilize water-in-oil emulsions and those which stabilize oil-in-water emulsions.- Gen erally emulsifying agents of the opposite type tend to work against and neutralize each other. Advantage is taken of this phenomenon when one wishes to break an emulsion. Thus, according to the classical theory,-

it is desired to break a waterrin oil: emulsion, stabilized by water-in-oil emulsifying agents, sufllc'ient oil-in-water type emulsifying agent is added to cause this effect. In accordance with the classical theory, the prior: art methods of resolving petroleum emulsions of the water-iu-oil type employ those emulsifying" agents characterized by being endowed with suihcient hydroph'ile roperty to be in fact oil-in-water type emulsifying agents. Hence,- sueli patents as De Groote et al., Patent No. 2,499,370; issued March 7, 1950, and De" Grooteet al., Patent No. 23-557,- 081, issued June 19, 1951-,- describeprocesses for breaking or resolving emulsions of the water-in-oilf type which employ certain oxyalkylatcd phenol-aldehyde resin demulsifierswhich contain a number of alky-leneoxy radicals (-always at least twice the number of phenolic? nuclei) sufficient to endow the demulsifier s' witli definite phile properties,- or" be" self eniulsifia ble o'r sel f dispersible; this condition is indicated as being the state where the hydrophilic end of the molecule predominates.-

Directly contrary to the teachings of the classical theory and prior art such as the De Groote et alt pate ts cited in the preceding paragraph, I have discovered that crude oil or petroleum emulsions of the water in--ei1 type can be broken orresolved by employing as the demulsif ying agents a class of chemical compounds which are non-emulsifiable or, when capable of emulsifying, form emulsions o f the water-in oil type. According: to my invention, an oxyalkylated phenol aldehyde resin; characterized by containing an alkyl phenol from a=definite class of phenols and containing a critical amount of oxyalkylene groups as the hydrophil-i'c component of themolecule, is employed as the demulsifie'r for'r'esolvin' petroleum emulsions of the water=in=oil type'in an economical and rapid manner. I V y v V The oxyalkylated phenolaldehyde resins constituting the demulsifiers used my invention can be'nianufacture'd by condensing an' appropriate alkyl phenol with a suitable aldehyde to forma resin" and then oxyalk'ylating the resin with certain oxyalkylerie' groups more particularly defined below; The alkyl phenols Wli'ich --ca'rl'- be' employed in producing the demu lsifiers of my invention are monocyclic phenols having an 'alk'yl substituent in the para-position containing not le'ss than 3 nor more than 2,973,340 Patented Feb. 28, 1951 carbon atoms. Examples of phenols Within the above definition include p-tertiairy butyl phenol, p-isopropyl phenol, p-tertiary amyl phenol, p-secondary amyl phenol and p-secondary butyl phenol. While para-substituted phenols must be employed to produce satisfactory demulsifiers for this invention, the presence of ortho-substituted phenols (e.g., up to about 12 percent) and of meta-substituted phenols (e.g., up to about 5 percent) included with the para-substituted phenol will not materially affect the results and in some instances'is desirable. A-Idehydes which may be employed are characterized by being reactive towards the phenols utilized and contain 1 to 8 carbon atoms per molecule. These aldehydes include, for example, formaldehyde, its trimer and linear polymer, in addition to acetaldehyde, propionic aldehyde, Z-ethylhexanal, butyraldehyde, ethylbutyraldehyde, mcthylbutyraldehyde, benzaldehyde', furfural, hept'aldehyde, and glyoxal.

In general the prior art methods of preparing resins to be oxyalkylated, as evidenced by the De Groote et al. Patents. Nos. 2,499,370 and 2,557,081 can be employed in this invention subject to the express modifications and preferences, indicated before and hereinafter, designed to insure the production of resins suited for my oxyalkylation step. The prior art resin preparation methods of the aforementioned De Groote et' al. patents are hereby incorporated into this disclosure in order to avoid extending the disclosure by detailed treatment of well-known rocedures. v

Resins suitable for oxyalkylat'ion to produce demulsifiers useful in my invention are characterized by being phenol-aldehyde resins which are susceptible to oxyalkylanon, fusible, soluble in acetone and certain other organic solvents but substantially insoluble in hydrocarbons and water. The resins have high molecular weights of the order of about 7,000 to 15,000, and usually about 10,000; on a phenol nuclei basis, my resins generally have about 40 to 1 00'pl'1enol nuclei per molecule. The general range of aldehyde to phenol ratios which produce suitable resins is about 0.70 to 1.5 moles of aldehyde per mole of phenol. I have found that particularly satisfactory resins are obtainable using an aldehyde to phenol mole ratio of about 1.0 to 12:1. I prefer to use one-half to one and one-half percent of concentrated hydrochloric acid as a catalyst for this condensation although sulfuric acid, phosphoric acid, sodium hydroxide, or potassium hydroxide canalso be employed. As with the catalyst, the" use of a solvent for the resin is not essential; however, as it permits handling the resin by pumping, facilita con tact between the reactants and tends to keep the" reaction mixture from becoming too" viscous, a solvent is employed ordinarily; Of the many solvents suitable, as indicated by prior art, xylene is preferred because it is inexpensive, may remain for use in the oxalkylation step anddoes not contaminate the demulsifier produced since the demulsifier can be employed as a solution in xylene. It is to be understood that the mixture of resin' andxyle'ne is not a true solution in the absolute sense of the word. The use of detergents has been found to aid the resinfor'ming'step and of the many suitable detergents, monoalkylated benzene monos'ulfefii'c acids or thesodiumsalts thereof, wherein the alkyl group contains 10 to 20 carbon atoms, have been found to be very efiective.

Onerriodifi'cafim of prior art methods of'resin preparation which has been found to enhance the resinsfor purposes of this invention entails refluxing the mixture remaining after separation of substantially all or the water content asthe last'step in the resin-forming procedure. This refluxingoperationgenerally'maybe' effected at about 0. and should extend-for at least about two'hours' during which time a" small aniount' of water is taken'overhead. Higher molecular-weight resins appear a; to be formed by-the refiuxingoperation, apparently resulting from greater polymerization and possibly from cross linking of various polymers.

The following are examples of the preparation of resins suitable for subsequent oxyalkylation to produce the demulsifiers useful in this invention. It is to be understood that the invention is not to be limited by the details recited in the examples.

EXAMPLES OF PHENOL-ALDEHYDE RESIN The para-tertiary butyl phenyl (Dow commercial grade) containing small amounts of meta-tertiary butyl phenol was mixed with the emulsifying agent and xylene by stirring and heating to 65 C. in a flask equipped for reflux operation. To the resulting solution the formaldehyde containing the hydrochloric acid catalyst was rapidly added with vigorous agitation. The contents of the reaction containerwere then heated to 90 C. at which point further heating was discontinued. An exothermic reaction became pronounced enough to carry the temperature up to the reflux temperature of the-xylene-water azeotrope. The reflux is quite vigorous at the start and gradually subsides. At this point heat is again applied to maintain reflux. Reflux of the xylene-water azeotrope is continued for 1% hours. water introduced with the formaldehyde and the water formed by reaction are removed as rapidly as posssible advantageously by raising the temperature. The time required for this operation runs from an hour to 3.5

At the end of this time the i hours depending on the rate of heating and equipment used. At the end of this water removal step the tem-' perature of the contents of the reaction vessel rises to the boiling point of xylene (MO-150 C.). At this point the Water is substantially all removed. The reaction mixture is then refluxed at the boiling point of the xylene for a minimum of 2 hours. The resulting xylene suspension of resin was used in subsequent oxyalkylation reactions as indicated below.

Example II Quantity Para-tertiary-amyl phenol moles 1.75 Formaldehyde, 37% (in water) do 1.75 Concentrated hydrochloric acid grari1s .3 Monoalkyl (C -C benzene monosulfonic. acid sodium salt grams 1 Xylene I do 200 The same procedure and the same type of equipment were used in making this'resin as described in Example I.

The xylene solution or suspension of this resin was employed in a subsequent oxyalkylation reaction to form demulsifiers useful in this invention.

Example III The same type of equipment and the same procedure was used in making this resin as described in Example I.

The formation of the alkyl phenol-aldehyde resin employing any of the other alkyl phenols mentioned as within the purview of thisinvention, either with formaldehyde or one of the other aldehydes, can be aceomweight components by the addition of methanol.

' plished in a manner substantially similar to the examples set out above.

' The product of the resin-forming step is a mixture containing some unreacted alkylphenol and polymer chains of various lengths. The presence of some unreacted alkyl phenol apparently has no effect on the product quality. The higher molecular weight fractions are not soluble in the xylene, and on standing precipitate out. The soluble portion of the resin solution without the precipitate is suitable for oxyalkylation, but is not as effective as the insoluble portion. In general no attempt is made to "separate the two portions. In the event the entire resin is to be employed in the subsequent oxyalkylation reaction, the quantity of oxyalkylene groups necessary can be determined by the quantity of phenol employed in the resin-forming step. For example, if x were the moles of phenol reacted and the total solution were to be oxyalkylated, the moles of oxyalkylene groups to be employed would be simply 0.75 to 1.75 times x, depending upon the choice of the particular ratio of oxyalkylene groups to phenolic nuclei, from the operable range, desired.

As noted above, the resin reaction mixture contains resin molecules of varying molecular weights. In special instances it may be desirable to produce the demulsifier by employing a resin with a particular range of molecular weights. The'resin product can be separated into various fractions by the following procedure: The precipitated or xylene insoluble portion can be separated by filtration or centrifuging. The soluble portion can then befurther separated by precipitated the higher molecular The precipitated material is then removed as above. The

' molecular weight of the original resin mixture or the fractions cannot be determined by the conventional cryoscopic or ebullioscopic methods because of their very high molecular weight. These methods are not reliable when resins above 1000-2000 M.W.. are used. Since my resins have molecular weights on the order of about 10,000 and higher these methods are obviously of no use. There- 'fore, by using such formulae as those proposed by Varcheidt [developed from Koebner or Flory the molecular weights of my resins were calculated.

, As with the resin-forming procedure, the general method of oxyalkylation is a well-known process as may be seen in the DeGroote et a1. patents previously cited. In general, such prior art methods can be employed to produce the demulsifiers used in my invention insofar as their temperatures, pressures, order and rate of reactant addition, catalysts, atmosphere, equipment, etc., conditions are concerned varied only by such exceptions, modifications and preferences which I expressly set forth. In order to avoid needless recitation of the prior art, the disclosure relating. to methods and conditions of oxyalkylation in the above cited De Groote et al. patents are hereby incorporated in this disclosure.

. The oxyalkylation reaction is carried out employing oxyalkylene groups corresponding functionally to the alpha-beta alkylene oxides containing not more than four carbon atoms. Examples of such groups are ethylene oxide, propylene oxide, alpha-beta butylene oxide, glycide and methyl glycide and mixtures thereof. I have found that results which are eminently satisfactory are obtained when the oxyalkylene groups employed are derived from a mixture. containing 35 to 45 mol percent ethylene oxide and 65 to 55 mol percent propylene oxide. However, a more generally preferred range of compositions of oxyalkylene groups extends from substantially pure propylene oxide to about 70:30 (mol ratio) mixture of ethylene oxide and propylene oxide. While percent of ethylene oxide may be used to oxyalkylate the resin and though it produces an excellent demulsifier for certain emulsions, demulsifiers produced with it do not appear to be Org. Chem. Ind. (U.S.S.R.) 3, 385-398 (1937).

'Z. angew. Chem. 46, 251'256 (1933). 'J. Azn. Chem. Soc. 65, 72 (1 43).

'as broadly applicable and effective as the demulsifiers produced employing the preferred oxide compositions.

In producing the oxyalkylated phenol-aldehyde resin demnlsifiers for use in my invention, it is of critical importance that the relative amount of oxyalkyl'ene groups used be controlled very carefully. In the event that an excess is used, the product produced falls outside the limits of the compositions of demulsifiers which may be used in my invention. As pointed out above, the demuL- sifiers useful in my invention are water-in-oil emulsifying agents or are non-emulsifying. As shown in the De Groote et a1. patents, there is a definite point when oxyalkylating phenol-aldehyde resins where the dominating characteristic of the demulsifier produced becomes hydrophilic. Such point is generally reached and the resulting demulsifier becomes definitely hydrophilic in character when two or more moles of oxyalkylene groups are reacted with the resin per one mole of phenolic nuclei present. -As should now be apparent from the previous characterization of the demulsifiers usefulin my invention, my demulsifiers can be produced only if the quantity of oxyalkylene groups employed in the oxyalkylation is materially less than two moles per mole of phenolic nuclei in the resin. The practical limiting ratio of oxyalkylene to phenolic nuclei is about 1.75:1; the operable range extends from about 0.75:1 to 1.75:1 withthe range of 1.25:1.0 to 1.70: 1.0 being preferred.

Of the prior art catalysts known to be useful for such oxyalkylations, I prefer to use sodium methoxide as it has been found to result in consistently satisfactory products. It is used in amounts sufiicient to neutralize any .acid catalyst present in the charge as a result. of the resin forming condensation, plus an additional 1 to 2 percent, based on the resin charge, to catalyze effectively the oxyalkylation reaction. A suitablemean temperature range is about 100 C. to 200 C. With agitation the reaction is effected in a relatively short. time of from several minutes to 6 to hours. While pressures of several hundred pounds per square inch gauge can be employed, practical considerations in commercial production indicate the use of a maximum pressure of about 50 ,p.s.i.g. The order of addition of reactants appears to be a matter of preference for the operator, but I have obtained con- 'sistent results and ease of operation when charging the resin and catalyst to the reaction vessel, heating to the reaction temperature and then adding the oxyalkylene groups.

The following are examples of the oxyalkylation step employed in producing the demulsifiers to be used in practicing my invention. it is not intended to limit the scope of this invention by the details disclosed in the examples.

OXYALKYLATION EXAMPLES Example IV V 7 Quantity Resin grams 135 Xylene d 65 Ethylene oxide 'mole 0.528 Propylene oxide do 0.600 Sodium methoxide grams '2 causing the temperature to go up to 165 C. where it "was maintained for the remainder of the reaction. When the pressure which resulted from the addition of gaseou's oxides had dropped back to'its initial value, the reaction was considered complete and the product removed. The final product was an 84.7 percent solution in xylene It should be understood that.

Numerous other samples were made employing resins obtained by following the procedure of Example I. The oxyalkylation procedure employed was the same "as in Example IV; however, the type of oxyalkylation was varied as "respects the oxyalkylene group introduced and the mol ratio of 'oxyalkylene group to phenolic nuclei in the resin used. Thirty-two such examples representative of the resins which can be produced are tabulated in Table III.

The present invention is concerned with treatment of petroleum emulsions by means of certain oxyalkylated resins which are water-in-oil type emulsifying agents or non-emulsifiable. The resins .which can be employed for oxyalkylation are characterized by having the phenolic component chosen from alkyl phenols containing one alkyl substituent in the para-position and the alkyl substituent having not less than 3 nor more than '5 carbon atoms therein. The oxyalkylated resins, in turn, consist of only those resins produced, utilizing any. of the phenols indicated, which have been oxyalkylated with oxyalkylene groups corresponding to alpha-beta oxyal'kylenes containing not over 4 carbon atoms per molecule, to the extent that they contain 0.75 to 1.75 moles of oxyalkylene group per mole of phenolic unit in the resin.

In practicing my invention for resolving petroleum emulsions of the water-in-oil type, a demulsifying agent or treating agent of the kind previously described is brought into contact with or caused to 'act upon the emulsion to be treated in any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical agent. My invention can be practiced using the demulsifying agents alone or in combination with other demulsifying procedure, such as the electrical dehydration process, orin combination with varying amounts of other demulsifying agents.

One common procedure which may be employed is to accumulate a quantity of the emulsion in a tank and conduct a batch treatment type of demulsification procedure to recover clean oil. In batch demulsification procedure, the demulsifier generally is mixed with the emulsion while the emulsion is being agitated. Various modifications, such as heating the emulsion'or withdrawing the emulsion from the bottom of the tank and reintroducing it admixed with demulsifierinto the top of the tank, can be employed.

In another common procedure which can be employed,

the de'r'nulsifier is introduced into well fluids at the well head or at some point between the well head and the final oil storage tank, by means of an adjustable proportioning oxides to phenolic unit of 1.37:1.

mechanisms or proportioning pump. Ordinarily the flow .of fluids through the subsequent lines and fittings sufiices to produce the desired degree of mixing of demulsifier and emulsion, although in some instances additional mixing devices can be introduced into the flow system. Heating devices can be incorporated in any system adopted. Other methods which can be used include employing the demulsifier directly to the crude oil-water mixture by adding it to the well and is known as down-the-hole demulsification. In all cases, it will be apparent, my process consists simply in introducing a relatively small proportion of demulsifier into a relatively large proportion of emulsion, insuring admixture of the demulsifier and emulsion, and allowing the mixture to stand until the undesirable water content of the emulsion separates and settles from the mass.

In testing demulsifiers, the efficiency or activity of the demulsifier compound is determined by observing the appearance of the treated emulsion; that is, the appearance of the treated emulsion is proportional to the efficiency or activity of the demu-lsifier compound. Freedom from cloudiness "in the oil indicates an elficient demulsifier. Comparisons of samples of emulsions treated with difierent dernulsifiers will indicate the relative efiicieney and activity of the demu-l'sifiers employed.

To demonstrate the effectiveness .of demulsifiersrm'a'de in accordance with my invention, various demulsifiers as derived from the examples above were made up in 2 percent concentration in xylene as solvent; 0.1 cc. of the demulsifier solution was then added to a 100 cc. sample of crude oil emulsion of the water-in-oil type secured from a well of the Sinclair Oil & Gas Companys Slimmer lease producing from the Bemis Pool north of Hayes, Kansas. Each sample was vigorously shaken 200 times and then observed. Results of this test are tabulated below.

NorE.(Samples 1 through 8 were made with resins formed of p-tertiary butyl phenol and formaldehyde subsequently oxyalkylated with a 40:60 mixture of ethylene oxide and propylene oxide.)

The appearance of sample emulsions was cloudy in all instances prior to addition of the demulsification agent. The above data emphasize the necessity'for observing the limitations as regards the molar ratio of oxyalkylation group to phenolic unit'of resin to be used in the oxyalkylation reaction; Examples 1, 2, 3 and 8 fall outside the critical limits of the ratio and were clearly unsatisfactory demulsifying agents.

In order to demonstrate the effectiveness of demulsifiers made in accordance with my invention, various demulsifiers as derived from the examples above were made up in 2 percent concentration in xylene as solvent. In certain instances, metaor ortho-substituted phenols were added to the phenol in the preparation of the resins. The demulsifiers were then tested by adding samples thereof to a 100 cc. sample of crude oil emulsion from the Bemis Pool as above identified. Demulsifier sample No. 6 of Table I, which was prepared in Example IV, was used as a standard. Other demulsifiers were then rated according to the percentage of demulsifier required to produce the same results as the standard in the same period of time. Table 11 below summarizes these tests.

TABLE II Position and type of Ratio, Rating, Sample 1 substituent in Resin 1 EtO PrO percent Employed Standard 40:60 40:60 110 40:00 1 10% m-cresol 40:60 Over 200 2% o-tertiary butyl phenol. 40:60 7% o-tertiary butyl phenol. 40:60 140 17% o-tertiary butyl phenol. 40:00 Over 200 100% p-Sec. amyl phenol 40:60 0

100% p-Sec. butyl phenol- 40:60 110 :30 1.56 50:50 122 20:80 112 0 100 109 1 Demulsifiers were made using oxyalkylene groups in amounts and in ratio to phenolic nuclei identical with the standard.

1 Difierenee between percent stated and 100 percent was p-tertiary butyl phenol in all samples.

definitely not hydrophile in character.

8 were not desirable as shown'in Examples C and F of Table II. All other demulsifiers fall within the limits established to produce satisfactory demulsifiers. The ratings disclose that demulsifiers produced in accordance with my instructions compare very favorably with my standard demulsifier.

In practicing my invention the demulsifier can be employed as made in solution. Since the solvent-free demulsifier is a hard brittle solid it must be used inconiunction with suitable solvents. Xylene is such a solvent as are petroleum hydrocarbons, benzene, toluene, alcohols, pine oil, carbon tetrachloride, and similar materials. Because 'such a small amount of demulsifying agent is included, apparent insolubility of the agent in the solvent vehicle utilized is immaterial. It should be understood that fsolvent as used herein is not intended to be taken in the strict sense, but rather indicates a liquid carrier means in those cases Where the resin is actually insoluble, i.e., in hydrocarbons.

The quantity, i.e., parts, of demulsifying agent required to resolve emulsions originating at dilferent sources will differ widely. ,The relative amount required for each emulsion can be determined by simple laboratory tests conducted by anyone interested in the problem. One suitable test would consist of adding varying amounts of demulsifier, in a suitable solvent, to measured samples of emulsion. Ten samples could be tested containing parts of demulsifier per part or emulsion of 1 to 500; 1 to 1000; 1 to 5000; l to 10,000; 1 to 15,000; 1 to 20,000 and so forth. The proper amount as determined by observing the appearance of the sample would be bracketed by two samples. A further test could then be made in a similar manner to determine the optimum amount of demulsifier to employ. Such routine determinations are within the skill of laboratory technicians generally, and it is not meant to imply that any experimentation is necessary to practice this invention.

I have found the use of from 1 to parts of demulsifying agent per 1000 parts of emulsion suflicient to resolve the emulsion within a time permitted by normal storage and settling capacity. Obviously, if settling capacity is limited, the time factor becomes very important and may justify the use of greater amounts of agent to speed the process. Such considerations are determined by. theconditions under which the demulsification process is operated.

The demulsifying agents produced for use in my demulsifying process are distinguished from known agents mainly by the limitation imposed on the relative quantity of oxyalkylene groups used to oxyalkylate the phenolaldehyde resins and the high molecular weight of the resins which are oxyalkylated. If two or more moles of oxyalkylene per mole of phenolic nuclei or unit of the resin are introduced, the agent resulting has definite hydrophile characteristics and is, therefore, outside the scope of demulsifying agents which can be employed in my invention. Demulsifying agents useful in my invention can be obtained only by oxyalkylating a phenol-aldehyde resin, which was formed using a phenol having one alkyl substituent of from three to five carbon atoms in the paraposition, with from about 0.75 to 1.75 moles of the defined oxyalkylene. Such demulsifying agents are very In fact the demulsifiers when solvent free are hard brittle solids and as such, of course, show no emulsion characteristics since they arewater insoluble and will not disperse. The only instance in which the demulsifiers show any surface activity is when they are dissolved in solvents such as xylene. In solution they are generally non-emulsifiable, or if forming an emulsion will invariably form water-iu-oil type emulsion. In no instance can these demulsifiers. be classed as self-emulsifying or self-dispersing. To demon-. strate this difference the data in Table III are offered.

1 Result not clear.

The test was used to determine whether the demulsifying agent formed an emulsion and, if so, the type formed, consisting of dissolving about 0.1 gram of the demulsifier in 5 ml. of xylene, adding 5 ml. of water and then shaking the mixture vigorously about 200 times. The sample was allowed to stand for about 16 hours, being examined then for the presence, if any, and type of emulsion. From the results tabulated it can be seen that demulsifiers used in my invention are non-emulsifiable in the vast majority of instances, and form water-in-oil type emulsions in the remainder of the examples. This test constitutes a method of determining whether a given demulsifier is within the scope of the present invention. That is, the demulsifiers of this invention are incapable of self-dispersing or forming an oil-in-water emulsion when one part of the demulsifier in 50 parts of xylene is shaken with 50 parts of water.

To demonstrate the difference between an oxyalkylated resin which does not have hydrophile properties, as in my invention, and such resins oxyalkylated to an extent to produce hydrophile properties the following test was made. A phenol-aldehyde resin made according to Example I using para-tertiary butyl phenol and formaldehyde was oxyalkylated with a 60-40 molar mixture of propylene and ethylene oxide. A series of samples was made as follows:

TABLE IV Mole oxide per mole phenol in resin Percent Emulsiflcatlon characteristic Sample N o.

33 Non-emulsifiable. 06 Some emulsion character but not complete. 09 Forms good oil-in-water emulslon.

The above samples were tested on fresh crude oil emulsion obtained from the Sinclair Oil & Gas Company, McGeorge No. 41 well, Gainsville, Texas. The well was producing from the Atkins formation. When a 4 percent solution of the above oxyalkylated compounds in xylene was added to ml. of emulsion and the mixture shaken 200 times in a bottle, the following results were obtained:

TABLE V Ml. of solution required to produce bright oil 0:2: (1)3gtween 0.2 and 0.5. More than 0.5.

More than 0.7. Do.

From the above it can be seen that the composition within the scope of my invention, Sample 1, is twice as effective as a borderline hydrophile product, i.e., Sample 2, and 5 to 7 times as eifective as oxyalkylated resins of definite hydrophile properties.

This application is a division of application Serial No. 478,921, filed December 30, 1954.

I claim:

1. A composition consisting essentially of an oxyalkylated phenol-aldehyde resin, said resin being the condensation product of (1) a phenol of the formula:

wherein R is an alkyl radical of about 3 to 5 carbon atoms, (2) about 0.70 to 1.5 moles of formaldehyde per mole of said phenol, (3) about 0.75 to 1.75 moles per mole of said phenol of an alpha-beta alkylene oxide of 2 to 4 carbon atoms, the phenol-aldehyde resin which is oxyalkylated being oxyalkylation susceptible, fusible and soluble in acetone but substantially insoluble in hydrocarbons and water, said oxyalkylated phenol-aldehyde resin containing about 40 to 100 phenolic nuclei per molecule and 1 part of said oxyalkylated phenol-aldehyde resin being incapable of dispersing or producing an oilin-water emulsion when shaken vigorously with 50 parts of water and 50 parts of xylene.

2. The composition of claim 1 wherein the moles of alpha-beta alkylene oxide per mole of phenol is about 1.25 to 1.70.

3. The composition of claim 1 wherein the moles of alphaabeta alkylene oxide per mole of phenol is about 1.25 to 1.70, and the alkylene oxide is a mixture of about 35 to 45 mole percent ethylene oxide and about 65 to 55 mole percent propylene oxide.

References Cited in the file of this patent V UNITED STATES PATENTS 2,0 60,41 0 

1. A COMPOUND CONSISTING ESSENTIALLY OF AN OXYALKYLATED PHENO-ALDEHYDE RESIN, SAID RESIN BEING THE CONDENSATION PRODUCT OF (1) A PHENOL OF THE FORMULA: 